Short Notes

K103

phys. stat. sol. ( a ) 63 , Kl03 (1981)

Subject classification: 1.2 and 14.4; 22.9
Department of Physics, University of Poona1)
Detection of Phase Transitions i n Polymers by TSC Technique
BY
J.P. JOG, S . J . WALZADE, and S.V. BHORASKAR
Thermally stimulated c u r r e n t s (TSC) have been used extensively to characterize
t r a p s /1 to 3/. Rather l e s s work has been c a r r i e d out in determination of phase
transitions and finding relations to the TSC s p e c t r a of a polarized dielectric.
We report h e r e about the phase transition temperatures in the co-polymer of
tetrafluoroethylene and hexafluoropropylene ( F E P type A (11 to 18)mo1'% of H F P

Dupont, USA) using thermally stimulated c u r r e n t measurements. This kind of

study in F E P h a s not s o far been found in literature. In this report we preferentially suggest the measurement of spontaneous c u r r e n t (TSC of virgin dielectric
samples in the absence of electric fields) f o r determining the g l a s s transition
temperature in polymers. This was concluded because the g l a s s transition temperature was found to b e largely affected by the strength of the field and the histo-

ry of charging.
In the present experiment the virgin sample was sandwiched between the
stainless s t e e l electrodes and the c u r r e n t was recorded in short circuit without
applying an electric field unless otherwise mentioned. The temperature was kept
uniform to an accuracy of +O. 5 OC throughout the sample and the electrodes, and
was monitored a t the sample by a chromel-alumel thermocouple. During the TSC
measurement the temperature was linearly varied with a r a t e of 6 . 4 K/min.
Fig. 1 shows the TSC in virgin, F E P , Perspec (PMMA), and Teflon ( F T F E ) .
The nature of the spontaneous c u r r e n t is found to remain the s a m e i n e a c h p o l y m e r .
The c u r r e n t remained negligibly small upto a certain temperature and increased
exponentially above this. Like the conductivity in the polymers the spontaneous
current 1 is also related to the activation energy E f o r the p r o c e s s by the relation
/4,

5/ I = I 0 exp(-E/kl), irrespective of the type of the metal-polymer-metal

contact /6/. H e r e E is a characteristic of the polymer and I is the pre-exponen0

tial constant. A plot of log I v e r s u s 1/1' should therefore be a straight line with a
1 ) 411007 Poona, India.

physica status solidi (a) 63

K104

TI"G)

Fig. 1. Spontaneous c u r r e n t thermogram in F E P ( 0), PMMA (-),

PTFE (

characteristic activation energy E . Such a plot for the c u r r e n t in Fig. 2 indicates not a single straight line, indicating that the polymer passes from the
glassy region into a rubbery region /7/. In between is the transition region accompanying the g l a s s transition temperature T
The segmental and main chain
g'
motion in the polymer begins a t T the a -transition.
g'

T for different samples determined from Fig. 2 are tabulated in Table 1.

g

In PMMA (syndiotactic) and P T F E the reported g l a s s transitions /7, 8; are a t

115 and 120 O C , respectively. Our results a r e in close agreement with these
values. In F E P we observe two transitions at 83 and 180 O C . We call them the
primary and secondary g l a s s transition temperatures T and T , respectively. Both
gl
of these w e name a%ansitions. T is in
g

close agreement with the value of 8010C reported by Turnhout /1/ f o r a s i m i l a r F E P

foil while T

is in close agreement with the

q -peak at g2130 OC observed by him in the

TSC of pre-polarized F E P . Moreover, his
charge thermograms also s t a r t decaying

Fig. 2. Semilogarithmic plot of current v e r s u s

1/T of
F E P ( 0 ), PMMA ( A ), PTFE ( 0 )

Short Notes
T a b l e

Experimentally calculated p a r a m e t e r s
property

FE P

g l a s s transition

83

PMMA

PTFE

115

120

gl

Tg (OC)

= 180

g2
activation
ene'rgy
E (eV)

glassy
state

0.53

0.14

0.22

rubbery
state

0.66

1. l l

0. n

at T =
= 2 4g20
8 C

relaxation time
(s)

109

177

near 180 OC remaining absolutely unaffected a t 80 OC. It is m o r e reasonable,

perhaps, to a s s u m e T

a t 180 OC to be the proper g l a s s transition where the

g2

molecular motions may become vigerous.

The activation energies in the g l a s s and rubber regions are tabulated (Table 1).

In F E P these are of the s a m e o r d e r s of magnitudes a s reported by Turnhout /1/

from depolarization measurements. The relaxation time z a t the g l a s s transition
temperature was determined from the relation
T = T o exp (E/kTI

where
2o =

2
g

k T /BE(exp(E/kT

1) ;

where E is the activation energy in glassy state and B and T are the heating
g
r a t e and g l a s s transition temperature, respectively.
It is observed that the relaxation time and the g l a s s transition temperature

are maximum for F E P which are indicative of i t s b e t t e r charge storage property

as also reported in the literature /9/.

It can be concluded that TSC is capable of

providing information regarding the molecular transitions in polymers.

The authors wish to thank Prof. M. R. Bhiday and Prof. A. S. Nigavekar f o r
their interest in the progress of the work. Tcanks a r e due to C. S.1. R . , New Delhi,

physica status solidi ( a ) 63

IU 06
f o r providing the financial assistance.
References

/1/ J. TURNHOUT, Thermally Stimulated Discharge in Polymer Electrets,

Elsevier, Amsterdam 1975.

/2/ G.M. SESSLERand J . E . WEST, J. appl. Phys. 47, 3480 (1976).

/3/ H.V. SEGGERN, J. appl. Phys. 50, 2817 (1979).
/4/ N. M. BIKALES, Characterization of Polymers, John Wiley and Sons, Inc.,
197l (Chap. 1).
/5/ R. DEWSBERRY, J. Phys. D 9, 265 (1976).
/6/ M. IEDA, G. SAWA, S. NAKAMURA, and Y. NISHO, J. appl. Phys. -946
2796 (1975).
/7/ J. M.G. COWIE, in: Po.ymers: Chemistry and Physics of Modern Materials,
Ed. K. STEAD, Billing and Sons Ltd., London 1973 (p. 203).
/8/ J. B. BIRKS, P r o g r e s s in Dielectrics, Vol. 2, Heywood and Co., Ltd.,
London 1960 (p. 31).
/9/ M.R. BHIDAY and S. RAO, P r a m h a 4, 271 (1975).
(Received October 13, 1980)